CN101958414B - Method for preparing anode of lithium sulfur battery - Google Patents
Method for preparing anode of lithium sulfur battery Download PDFInfo
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- CN101958414B CN101958414B CN2010105138664A CN201010513866A CN101958414B CN 101958414 B CN101958414 B CN 101958414B CN 2010105138664 A CN2010105138664 A CN 2010105138664A CN 201010513866 A CN201010513866 A CN 201010513866A CN 101958414 B CN101958414 B CN 101958414B
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- sulphur
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Abstract
The invention relates to a method for preparing an anode of a lithium sulfur battery, which comprises the following steps of: 1) pretreating a metal sheet: cutting the metal sheet with neat surface into a circular sheet, cleaning by using cotton balls absorbed with acetone, performing ultrasonic cleaning by using distilled water, taking out, and airing; and 2) preparing a carbon sulfur composite material: putting the treated metal sheet into a cavity of a sputtering device, carrying carbon disulfide vapor into the cavity by using sputtering gas, forming plasma by using the sputtering gas, sputtering high-purity graphic target by using the sputtering gas, depositing a carbon film on the pretreated metal sheet, decomposing the carbon disulfide vapor in the plasma formed by the sputtering gas, depositing the generated sulfur and carbon sulfur groups in the carbon film to realize sulfur doping, and preparing the carbon sulfur composite material through deposition, wherein the metal sheet on which the carbon sulfur composite material is deposited is the anode of the lithium sulfur battery. The preparation method is favorable for improving the cyclical stability of the battery, and can avoid reduction of conductivity of the anode caused by an adhesive and shorten the preparation period of the anode of the battery.
Description
Technical field
The present invention relates to a kind of preparation method of lithium-sulphur cell positive electrode, belong to field of electrochemical batteries.
Background technology
The lithium-sulfur cell negative pole is a metal lithium sheet, and the anodal sulphur that adopts is as active material.The lithium ion that negative pole produces during discharge diffuses to anodal and reaction of Salmon-Saxl generates lithium sulfide.Under applied voltage, above-mentioned electrode reaction can reversely be carried out, thereby realizes battery charge.The Theoretical Mass specific capacity of elemental sulfur is 1675mAh/g, and the transition metal oxide LiCoO that common lithium ion battery adopts
2, LiNiO
2And LiMn
2O
4Theoretical specific capacity is respectively 275 mAh/g, 274 mAh/g and 148 mAh/g.In addition, sulphur is cheap.Along with the lifting that portable type electronic product requires battery lightness, cost degradation and superperformance, the lithium-sulfur cell development prospect is wide.
Yet, because sulphur is that (conductivity is 5 * 10 25 ℃ the time for electronics and ion insulator
-30Scm
-1), participate in anodal reaction in order to make sulphur, need to promote the conductivity of sulphur, the method that adopts usually is that elemental sulfur and conductive agent (like acetylene black) are carried out that mechanical ball milling mixes or sulphur and conductive agent are heated jointly.After in the mixture of sulphur and conductive agent, adding adhesive (like PEO PEO or Kynoar PVDF), in appropriate solvent, be modulated into pasty state, blade coating promptly makes lithium-sulphur cell positive electrode after the drying on metal collector.
There are some problems in the lithium-sulphur cell positive electrode that method for preparing goes out; Positive pole for the preparation of mechanical ball milling method; Owing to have only sulfur granules surface energy conduction; Sulfur granules inside can not be conducted electricity and simple ball-milling method can not make the sulfur granules below the micron order, and this makes that the utilance of sulphur is not high and the battery discharge specific capacity is lower; Simultaneously, lose owing to the anodal sulphion that reacts generation is soluble in the electrolyte, this causes the battery cyclical stability relatively poor; In addition, the adhesive in the positive electrode is generally high molecular polymer, their poorly conductive, and this can further reduce battery performance.For the positive pole of sulphur and the common heating preparation of conductive agent,, be difficult to realize making that the sulfur content that can conduct electricity is not high by the evenly compound of sulphur and conductive agent that this causes the battery discharge specific capacity not high through flowing because the viscosity of the sulphur of heating and melting is higher; Simultaneously, the sulphion that anodal reaction generates is soluble in the electrolyte and loses, and this causes the battery cyclical stability relatively poor; In addition, the high molecular polymer with poorly conductive in the positive pole is an adhesive, and this further reduces battery performance.
To the problems referred to above, some researchers attempt solving.People's [electrochemistry such as king's Chong of Xiamen University; 2010; 16 (2): 168-171] prepared the porous carbon gel, after it is mixed altogether heat with elemental sulfur, then with gained mixture and conductive agent and adhesive mixing and ball milling; After be coated on the aluminum foil current collector after mixture processed slurry, promptly make lithium-sulphur cell positive electrode after the drying.Carbon gel absorption sulphur is dissolved in electrolyte and has played certain effect suppressing in the positive pole sulphion; But; The carbon gel has loose structure and does not have high conductivity owing to it; The conductivity of the mixture that sulphur and carbon gel contact closely will be lower than the conductivity of the mixture that sulphur and conductive agent directly contact, and this is unfavorable for promoting the conductivity of sulphur.In addition, contain the adhesive of poorly conductive in the positive pole, it can reduce anodal conductivity, makes battery performance descend.Problem to the higher and difficult dispersion of viscosity of molten sulfur in sulphur and the common hot method of conductive agent; People such as the Zhao Chunrong of University of Science & Technology, Beijing [battery; 2010,40 (1): 6-9] attempted the normal temperature vacuum impregnation technology and prepared sulphur and mesoporous carbon mixture, they are with the mesoporous charcoal of carbon disulfide solution soaking that is dissolved with elemental sulfur; After carry out vacuum filtration, the sulphur of separating out is adsorbed by mesoporous charcoal.Sulphur that makes and mesoporous carbon mixture again with conductive agent and adhesive mechanical mixture, mixture is coated on the aluminium foil after being modulated into slurry, promptly makes lithium-sulphur cell positive electrode after dry 10 hours.Mesoporous charcoal is dissolved in electrolyte and has played certain effect suppressing anodal sulphion the suction-operated of sulphur in the positive pole; But; Mesoporous charcoal has loose structure and does not have satisfactory electrical conductivity owing to it; The conductivity of the mixture that sulphur and mesoporous charcoal closely contact will be lower than the conductivity of the mixture that sulphur and conductive agent directly contact, and this is unfavorable for the lifting of sulphur conductivity.In addition, contain the adhesive LA132 (a kind of aqueous binder) of poorly conductive in the positive pole, it can reduce anodal conductivity, makes battery performance descend.
Summary of the invention
Problem to be solved by this invention is to above-mentioned prior art and the preparation method of a kind of lithium-sulphur cell positive electrode of proposing; It mixes sulphur in depositing carbon film on the sheet metal collector; Preparation sulphur carbon composite; The sheet metal that deposits this composite material is lithium-sulphur cell positive electrode, the manufacturing cycle that it can be avoided the decline of the anodal conductivity that adhesive causes and can shorten anode.
The present invention by the problem of the above-mentioned proposition of solution the employing solution be: a kind of preparation method of lithium-sulphur cell positive electrode is characterized in that including following steps:
1) preliminary treatment of sheet metal:
The sheet metal of surfacing is cut into the disk that diameter is 11-14mm,, used the distilled water ultrasonic cleaning then 2-4 minute, dry after the taking-up with inhaling cotton balls wiping disk 1-2 minute that acetone is arranged;
2) preparation of sulphur carbon composite:
The step 1) processed sheet metals is put into the cavity of sputter equipment; The high purity graphite target is adopted in sputter, and sputter gas is carried into the carbon disulfide steam in the cavity of sputter equipment, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, sedimentation time is 7-8 hour, promptly makes the sulphur carbon composite, and the sheet metal that deposits this sulphur carbon composite is lithium-sulphur cell positive electrode.
Press such scheme, described sheet metal is nickel foil, aluminium foil or Copper Foil.
Press such scheme, described sputter equipment is magnetically controlled DC sputtering device or rf magnetron sputtering device.
Press such scheme, described sputter gas is argon gas or nitrogen.
The present invention mixes sulphur in the depositing carbon film on the sheet metal collector, produce because the sulphur that mixes is decomposed by the carbon disulfide steam, thereby can obtain small size sulphur.And the Sulfur capacity that is in gaseous state is prone to diffusion motion, thereby realizes that sulphur evenly disperses in carbon base body.Common mechanical mixing reaches altogether, and hot mixing method is a raw material with large-sized elemental sulfur; And sulphur is in solid-state or liquid in two kinds of methods; Be difficult for diffusion motion, cause the degree of scatter of sulphur less, this causes the utilance of sulphur and battery discharge specific capacity not high; By contrast, the lithium-sulphur cell positive electrode of the present invention's preparation can obtain high battery discharge specific capacity because of the good dispersiveness of sulphur.In addition, because sulphur content is dispersed in the carbon base body and coated by carbon, this structure can constrain in positive pole with the sulphion in the positive pole reaction, suppresses it and is dissolved in electrolyte and loses, and this helps the lifting of battery cyclical stability.In addition, do not contain the adhesive of poorly conductive and drying for a long time in the positive pole of the present invention preparation, thereby the present invention can avoid the decline of the anodal conductivity that adhesive causes and can shorten the manufacturing cycle of anode.
Embodiment
Below in conjunction with embodiment the present invention is described further, but can not be as to qualification of the present invention.
Embodiment 1:
The Copper Foil of surfacing is cut into the disk that diameter is 11mm,, used the distilled water ultrasonic cleaning then 3 minutes, dry after the taking-up with inhaling the cotton balls wiping disk 2 minutes that acetone is arranged;
Copper Foil after handling is put into the cavity of magnetically controlled DC sputtering device; The target that sputter is adopted is that diameter is the high purity graphite target of 50mm; Distance between target and the Copper Foil is adjusted to 60mm, adopts nitrogen that the carbon disulfide steam is carried in the cavity, and the air pressure that feeds in the preceding cavity of gas reduces to 1 * 10
-3Pa; The total flow of regulating nitrogen and carbon disulfide steam during ventilation is 20sccm (ml/min under the standard state); The control cavity internal pressure is 0.6Pa, and sputtering power is adjusted to 150W, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, deposit and make the sulphur carbon composite after 7 hours, after the cooling, the Copper Foil that deposits this composite material is lithium-sulphur cell positive electrode.
Embodiment 2:
The nickel foil of surfacing is cut into the disk that diameter is 13mm,, used the distilled water ultrasonic cleaning then 3 minutes, dry after the taking-up with inhaling the cotton balls wiping disk 2 minutes that acetone is arranged;
Nickel foil after handling is put into the cavity of magnetically controlled DC sputtering device; The target that sputter is adopted is that diameter is the high purity graphite target of 50mm; Distance between target and the nickel foil is adjusted to 60mm, adopts argon gas that the carbon disulfide steam is carried in the cavity, and the air pressure that feeds in the preceding cavity of gas reduces to 1 * 10
-3Pa; The total flow of regulating argon gas and carbon disulfide steam during ventilation is 30 sccm; The control cavity internal pressure is 0.8Pa, and sputtering power is adjusted to 160W, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, deposit and make the sulphur carbon composite after 7 hours, after the cooling, the nickel foil that deposits this composite material is lithium-sulphur cell positive electrode.
Embodiment 3:
The aluminium foil of surfacing is cut into the disk that diameter is 12mm,, used the distilled water ultrasonic cleaning then 3 minutes, dry after the taking-up with inhaling the cotton balls wiping disk 2 minutes that acetone is arranged;
Aluminium foil after handling is put into the cavity of rf magnetron sputtering device; The target that sputter is adopted is that diameter is the high purity graphite target of 50mm; Distance between target and the aluminium foil is adjusted to 50mm, adopts nitrogen that the carbon disulfide steam is carried in the cavity, and the air pressure that feeds in the preceding cavity of gas reduces to 1 * 10
-3Pa; The total flow of regulating nitrogen and carbon disulfide steam during ventilation is 50 sccm; The control cavity internal pressure is 1.2Pa, and sputtering power is adjusted to 170W, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, deposit and make the sulphur carbon composite after 8 hours, after the cooling, the aluminium foil that deposits this composite material is lithium-sulphur cell positive electrode.
Embodiment 4:
The nickel foil of surfacing is cut into the disk that diameter is 14mm,, used the distilled water ultrasonic cleaning then 3 minutes, dry after the taking-up with inhaling the cotton balls wiping disk 2 minutes that acetone is arranged;
Nickel foil after handling is put into the cavity of rf magnetron sputtering device; The target that sputter is adopted is that diameter is the high purity graphite target of 50mm; Distance between target and the nickel foil is adjusted to 50mm, adopts argon gas that the carbon disulfide steam is carried in the cavity, and the air pressure that feeds in the preceding cavity of gas reduces to 1 * 10
-3Pa; The total flow of regulating argon gas and carbon disulfide steam during ventilation is 60 sccm; The control cavity internal pressure is 1.5Pa, and sputtering power is adjusted to 180W, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, deposit and make the sulphur carbon composite after 8 hours, after the cooling, the nickel foil that deposits this composite material is lithium-sulphur cell positive electrode.
For composition and the performance that characterizes the lithium-sulphur cell positive electrode of preparing; Lithium-sulphur cell positive electrode with embodiment 2 preparations is a sample; Adopt energy disperse spectroscopy that anodal material composition is detected, the EDS that draws (energy dispersion spectrum) shows and contains sulphur and two kinds of elements of carbon in the positive electrode that the atomic percent of sulphur and carbon is 19.37:80.63; Mass percent is 39.07:60.93, and this shows that sulphur has mixed in the carbon base body.In order to characterize this anodal chemical property, be positive pole with this positive pole sample, with the metal lithium sheet negative pole, electrolyte adopts the LiCF of 1mol/L
3SO
3/ (DOL+DME) (volume ratio of DOL and DME is 1:1); Barrier film is a Celgard2046 type film, and assembled battery in the argon gas atmosphere glove box is carried out charge-discharge test with the battery that assembles on the electric battery test system of indigo plant; Deboost is 2.8-1V, and charging and discharging currents density is 0.2mA/cm
2First discharge specific capacity is 975mAh/g, and the specific capacity after the charge and discharge cycles 40 times is 723mAh/g, and this lithium-sulphur cell positive electrode that shows this method preparation has high specific discharge capacity and good cyclical stability.
Claims (4)
1. the preparation method of a lithium-sulphur cell positive electrode is characterized in that including following steps:
1) preliminary treatment of sheet metal:
The sheet metal of surfacing is cut into the disk that diameter is 11-14mm,, used the distilled water ultrasonic cleaning then 2-4 minute, dry after the taking-up with inhaling cotton balls wiping disk 1-2 minute that acetone is arranged;
2) preparation of sulphur carbon composite:
The step 1) processed sheet metals is put into the cavity of sputter equipment; The high purity graphite target is adopted in sputter, and sputter gas is carried into the carbon disulfide steam in the cavity of sputter equipment, and sputter gas is at the direct voltage of sputter equipment input or radio-frequency voltage effect formation plasma down; Sputter gas sputter high purity graphite target after the ionization; Depositing carbon film on pretreated sheet metal, in depositing carbon film, the carbon disulfide steam that is carried in the cavity by sputter gas is decomposed in the plasma that sputter gas forms; Decompose the sulphur and the sulphur carbon-based group that generate and be deposited in the carbon film, realize mixing sulphur; Thereby mix sulphur when being implemented in depositing carbon film, sedimentation time is 7-8 hour, promptly makes the sulphur carbon composite, and the sheet metal that deposits this sulphur carbon composite is lithium-sulphur cell positive electrode.
2. by the preparation method of the described a kind of lithium-sulphur cell positive electrode of claim 1, it is characterized in that described sheet metal is nickel foil, aluminium foil or Copper Foil.
3. by the preparation method of claim 1 or 2 described a kind of lithium-sulphur cell positive electrodes, it is characterized in that described sputter equipment is magnetically controlled DC sputtering device or rf magnetron sputtering device.
4. by the preparation method of claim 1 or 2 described a kind of lithium-sulphur cell positive electrodes, it is characterized in that described sputter gas is argon gas or nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163712B (en) * | 2011-03-16 | 2013-03-13 | 天津大学 | Preparation method of sulfur positive material of lithium sulfur battery |
| CN102280614B (en) * | 2011-07-07 | 2013-08-28 | 天津大学 | Preparation method of sulfur positive electrode of lithium sulfur battery |
| CN103840141B (en) * | 2012-11-23 | 2016-07-20 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell integrated electrode and preparation method thereof |
| CN105826081A (en) * | 2016-06-13 | 2016-08-03 | 东南大学 | Titanium-dioxide-based nanorod array counter electrode and preparation method and application thereof |
| CN108493402B (en) * | 2018-04-12 | 2021-04-02 | 太原科技大学 | Method for preparing lithium-sulfur battery positive plate by ion beam sputtering technology |
| CN108565394B (en) * | 2018-04-12 | 2021-04-02 | 太原科技大学 | Method for preparing lithium-sulfur battery positive plate by utilizing magnetron sputtering technology |
| CN110957472B (en) * | 2019-12-20 | 2021-03-30 | 电子科技大学 | Preparation method of lithium-sulfur battery positive electrode material |
| CN111092207A (en) * | 2019-12-20 | 2020-05-01 | 深圳天元羲王材料科技有限公司 | Positive electrode material, preparation method thereof and lithium-sulfur battery |
| CN113540420B (en) * | 2021-07-12 | 2022-08-23 | 成都博时捷科技有限公司 | Preparation method of lithium-sulfur battery positive electrode material and lithium-sulfur battery |
| CN114975974A (en) * | 2022-07-11 | 2022-08-30 | 焦作聚能能源科技有限公司 | High-energy-density graphite composite material, preparation method thereof and lithium ion battery |
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| CN101378120A (en) * | 2008-10-13 | 2009-03-04 | 武汉工程大学 | Method for preparing lithium battery anode |
| CN101740787A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Metal particle-amorphous diamond composite anode for fuel cell and preparation method thereof |
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| JP2002329495A (en) * | 2001-05-01 | 2002-11-15 | Matsushita Electric Ind Co Ltd | Lithium secondary battery and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101378120A (en) * | 2008-10-13 | 2009-03-04 | 武汉工程大学 | Method for preparing lithium battery anode |
| CN101740787A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Metal particle-amorphous diamond composite anode for fuel cell and preparation method thereof |
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| JP特开2002-329495A 2002.11.15 |
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